Testing my RDX rxn:

[Mr Cool]

Firstly, I know there are countless threads on RDX, but I thought I'd start a new one, because this method is slightly different to others. If it works, it will require no acetic anhydride, and no nitric acid. I'll try it tomorrow and tell you the results (I'm going to bed after I've typed up this).

There has been some talk recently on using Ca(NO3)2 with H2SO4 in nitrations, since the CaSO4 formed is insoluble. I was going to make nitric acid like this, but I figured that with the 19mL of H2SO4 and 59g of Ca(NO3)2 needed, any HNO3 made would be absorbed by the CaSO4, and I wouldn't be able to pour it off. Therefore, it would require distillation, and it therefore wouldn't help. But then I thought: the CaSO4 is INSOLUBLE. This means that there would be no Ca++ or SO4-- ions in the solution, so it would behave just like HNO3. If I used an excess of Ca(NO3)2, then there would be no H2SO4 present to interfere with the reaction. So would it work to just mix the Ca(NO3)2 and H2SO4, and use this instead of nitric acid? Well, I'll find out tomorrow!

I'll use 18mL of H2SO4, 59g of Ca(NO3)2, 14g of hexamine, and 16g of NH4NO3. This means that the Ca(NO3)2 is in excess to make the HNO3, and the HNO3 is in great excess in the reaction as a whole.
The equation will be:

2 Ca(NO3)2 + 2 H2SO4 + C6H12N4 + 2 NH4NO3 ---> 2 C3H6N6O6 + 6 H2O + 2 CaSO4

I'll put up more detailed information, and results, when I'm less fatigued.

Comments? Criticisms? I'd love to hear them!

[kingspaz]

after reading the calcium nitrate topic i thought of pretty much the same thing!!! although i haven't any plans yet i was considering making RDX aswell.would the RDX crystalise out of the solution as it formed since the solution is water not acid or would it stay in solution due to excess calcium nitrate?
please let me know how you get on.

[ALENGOSVIG1]

I just tried it. Ill heat it tommorow and attempt to precipitate it becuase its getting late here. Ill let you all knmow how it goes?

[John456]

I just tried this with Mr. Cool's measurements (18mL of H2SO4 straight from the hotplate, 59g of Ca(NO3)2, 14g of hexamine, and 16g of NH4NO3). I mixed the Calcium Nitrate and the H2SO4 and let them stand for about 15 mins, then poured off the HNO3. I then cooled it to about 15*C and began adding hexamine. It foamed like making RDX with distilled acid so i thought i was the right track. I added portions of NH4NO3 in between hexamine too. I stirred for about half an hour till it all dissolved, then heated it to 55*C for 25 minutes. I poured the whole thing into 400mL of distilled water and after about 10 mins a little sheet of crystals settled to the bottom, not more than half a gram im guessing. Its been about 3 hours and theres still no change so my guess is that some water is produced in the Ca(NO3)2 reaction.

Edit: I just tried making PETN with this acid and it worked!! I used 24g of pentaerythritol (bought) instead of the NH4NO3 and hexamine. approximately 20g of PETN was made!! Im assuming its PETN, im going to detonate it tommorrow.

[This message has been edited by John456 (edited July 06, 2001).]

[wantsomfet]

You're sure it worked? 20g PETN from 24g PE would be an extremely bad yield...

This is what Urbanski says to the nitrating ability of different nitrates:
AgNO3 > KNO3 > NaNO3 > NH4NO3 > Pb(NO3)2 > Ba(NO3)2
Also catalysts like AlCl3, FeCl3, SiCl4 and BF3 may be used.

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[Mr Cool]

You were able to pour off the acid? Surprising. I think that you still had H2SO4 because not all of the nitrate had reacted. What I would do is this:

Mix the ANHYDROUS POWDERED calcium nitrate and 98% sulphuric acid, and cool it to about 20*C. Then stir in the anhydrous NH4NO3. This will convert any remaining H2SO4, as well as contrinute to the yield. Then I'd cool this to about 15*C, and slowly add the hexamine while stirring and keeping the temp. below 30*C. After the addition, stir it for 5 minutes and slowly raise the temperature to 50*C. Hold it there, while stirring, for 5-10 minutes, let it cool to room temperature, and pour it into lots of ice/water. Purify as normal. I assume CaSO4 is insoluble in acetone, so it can be filtered out. A bit of lithium nitrate will apparently help the RDX to form.

I'll try this now, and let you know how I get on. It *should* make 44.4 grams of A-type RDX from 14 grams of hexamine, but I'd be happy with 10.

[Mr Cool]

I'll be starting in a few minutes. The NH4NO3 and Ca(NO3)2 are in the oven, the H2SO4 is boiling, and the hexamine is in a dessicator and has been since yesterday. So there should be very little water in the reaction.
And if you were to use a 100% excess of Ca(NO3)2 and H2SO4, then even after the water is made by the reaction, the HNO3 is still at 70%. I can't remember how much excess I used when working out the proportions, I think it was about 20% so I might use more acid mixture. I'll use the equivalent of 50mL of HNO3, that's about 98% excess. It will require 32mL of H2SO4 and 100g of Ca(NO3)2.

Wish me luck everyone!

[10fingers]

Interesting experiment. Good Luck!

[John456]

At first the thing was practically solid but after 15 mins a layer of liquid came to the top which i poured off, and for the rest i pushed the solid with a spoon and the liquid went into the spoon. I know 20g of PETN is bad for 24g of PE but at least it worked, im going to experiment with different amounts hopefully today. By the way, i detonated 10g of the PETN and it worked beautifully.

[Mr Cool]

I got 500g of PE recently. PETN is good stuff isn't it?!
I haven't been able to do it yet, I've been out all day, but I might do it later on and maybe post results this evening.

[ALENGOSVIG1]

Where did you aquire the PE Mr.Cool?

[Mr Cool]

A forum member managed to get it from a UK chem company, by doing lots of lying ("my company is relocating, so you'll have to send it to my home address"!). I won't reveal his name, because loads of people will probably hassle him about it if I do.

[ALENGOSVIG1]

Well, whoever the person is, if they'd be nice enough to email me at alengosvig@yahoo.com that'd be great.

[John456]

I got my PE by saying i was experimenting with low-density resins (I live in the US). I was able to get about 5 kg, yes PETN is good stuff =) I tried the experiment again with RDX by the way and still nothing...

[wantsomfet]

Where do you order it? pyrotek?

[This message has been edited by ALENGOSVIG1 (edited July 06, 2001).]

[John456]

Nah, i wouldnt order it from Pyrotek. Its a raw materials supplier for plastics. I wont say the name to be safe, sorry. Also, Mr. Cool, question: Does your PE always seem wet no matter what you do with it (dry it in an oven, in a dessicator etc)

[CyclonitePyro]

Calcium nitrate seems to be the unknown chemical for me, all pyro suppliers don't carry it and I don't know of any common uses for it, I kinda hope there aren't any so I don't feel like an ass for not knowing if there are any. Could someone please tell me someway of obtaining this chem.

[ALENGOSVIG1]

fertilizer. i got mine from my hydroponics supplier a few months back. its 100% pure.

[Mr Cool]

My PETN is incredibly fine, and therefore takes a long time to dry. I haven't put it in the oven or dessicator, but after about 2 warm days it is nearly dry. It's in a thin layer, and "broken up" to give it a large surface area. Even with this water content, it is easily detonatable in an exploding bridgewire cap, or in a cap with 0.3g of HMTD.
My PETN is VERY slightly yellow. What about yours? I was expecting a pure white. It was well washed, neutralised, and recrystalised from alkaline acetone, so I don't think it's NO2.

[John456]

Mine is always pure white after washing but it turns a slight dark orangy color after drying. It takes a hell of a long time to dry though, i can only dry it by spreading it out over a couple square feet, or else it cakes up. I can detonate it no matter how wet it is thoough, as long as it isnt soaking.

[PHILOU Zrealone]

Wantsomfet:
The sequence of nitrates you have exposed is true only in the case of nitration via nucleophilic substitution of an organohalide

AgNO3 + CH3Br --(appropriate solvant)-> AgBr + CH3NO3

Ag>or equal to Li>K>Na>...


For the others yes Ca(NO3)2 is really hygroscopic and water contain can be a problem, but the major problem comes from thermodynamics:
How the hell do you want a solid to dissolve in a media if on its surface forms imediately an unsoluble layer that thickens fast slowering fast the solubilisation; soon the cristal can not dissolve anymore but by solid/solid migration what is very slow and can take ages-centuries!
Undoubtly most of the Ca(NO3)2 is unused and thus there remains a lot of H2SO4 in the media what is bad for RDX synthesis!
I remind you that CaSO4 is unsoluble in water (wel little soluble since nothing is unsoluble) this "unsolubility" is increased if a common ion is present in the media...and what is strong H2SO4 but a powerfull source of SO4(2-)??

Now to help a bit instead of saying it was a stupid thing to do:
You can used this process with a little modification to produce nitric acid more concentrated than the original one without need of a distillator:
If you have concentrated H2SO4 more than your HNO3- and only if you have it!
-Mix hot medium conc or conc HNO3 and saturate it with Ca(NO3)2 by strong stirring.Heat it long to be sure it is saturated. Cool it until ambiant temp some Ca(NO3)2 cristals will come out proof of the saturation, filter them. In the clear solution can now be inserted under stirring the conc H2SO4 ( it has to be in minor quantity as compare to Ca(NO3)2 dissolved).
Then in your solution you will have a cloud of CaSO4 pure HNO3 more concentrated and some Ca(NO3)2 leftover.


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